JPH02125830A - Cu-zn series alloy material having excellent stress corrosion cracking resistance and its manufacture - Google Patents
Cu-zn series alloy material having excellent stress corrosion cracking resistance and its manufactureInfo
- Publication number
- JPH02125830A JPH02125830A JP27734588A JP27734588A JPH02125830A JP H02125830 A JPH02125830 A JP H02125830A JP 27734588 A JP27734588 A JP 27734588A JP 27734588 A JP27734588 A JP 27734588A JP H02125830 A JPH02125830 A JP H02125830A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- corrosion cracking
- stress corrosion
- core material
- series alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 230000007797 corrosion Effects 0.000 title claims abstract description 25
- 238000005260 corrosion Methods 0.000 title claims abstract description 25
- 238000005336 cracking Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000011162 core material Substances 0.000 claims abstract description 22
- 238000009792 diffusion process Methods 0.000 claims abstract description 21
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical class [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 6
- 229910017518 Cu Zn Inorganic materials 0.000 claims description 16
- 229910017752 Cu-Zn Inorganic materials 0.000 claims description 16
- 229910017943 Cu—Zn Inorganic materials 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 5
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract 2
- 239000010949 copper Substances 0.000 description 21
- 238000007747 plating Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910001369 Brass Inorganic materials 0.000 description 3
- 229910002535 CuZn Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000007779 soft material Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910001015 Alpha brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 101100008046 Caenorhabditis elegans cut-2 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐応力腐食割れ性に優れたＣｕＺｎ系合金材料
とその製造方法に関し、特にＣｕ−Ｚｎ系合金の優れた
加工性と機械的特性とを活し、応力腐食割れ感受性を大
巾に低減したものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a CuZn alloy material with excellent stress corrosion cracking resistance and a method for producing the same, and in particular to the excellent workability and mechanical properties of the Cu-Zn alloy. By taking advantage of this, the susceptibility to stress corrosion cracking is greatly reduced.
Ｚｎを２０〜３５ｗ１％含む黄銅合金は高強度で加工性
が優れた低価格銅合金材料として知られており、各種端
子、コネクター、配線器具部品。Brass alloy containing 20-35 w1% Zn is known as a low-cost copper alloy material with high strength and excellent workability, and is used in various terminals, connectors, and wiring equipment parts.
自動車ラジェーターや各種熱交換器等に広く使われてい
る。しかしながら黄銅合金は古くから知られているよう
に応力腐食割れ感受性が高く、応力腐食割れによる事故
が数多くみられ、信頼性や材料効率を追求する設計や用
途において大きな障害となっている。Widely used in automobile radiators and various heat exchangers. However, as has been known for a long time, brass alloys are highly susceptible to stress corrosion cracking, and many accidents due to stress corrosion cracking have been observed, posing a major obstacle in designs and applications that pursue reliability and material efficiency.
応力腐食割れは材料に作用する応力と腐食環境の相互作
用による現象と考えられており、材料に作用する応力を
小さくするか、使用前に低温焼鈍により残留応力を除去
する方法が採用されている。また材料側からは各種の添
加元素による改善方法も提案されているが、環境条件に
見合って応力腐食割れ感受性の小さい材料、例えば純銅
系の材料の選択を余儀なくされる場合もある。またＮｉ
やＣｕ等の被覆層を形成し、腐食環境を遮断する方法も
提案され、一部で採用されている。Stress corrosion cracking is thought to be a phenomenon caused by the interaction between the stress acting on the material and the corrosive environment, and methods are used to reduce the stress acting on the material or remove residual stress by low-temperature annealing before use. . In addition, from the material side, improvement methods using various additive elements have been proposed, but depending on the environmental conditions, it may be necessary to select a material with low stress corrosion cracking susceptibility, such as a pure copper-based material. Also Ni
A method of forming a coating layer of , Cu, etc. to block the corrosive environment has also been proposed and has been adopted in some cases.
しかしこれ等の方法は、環境によっては応力腐食割れを
防止する効果が不十分な場合があり、黄銅の高強度を加
工性の優れた低価格材料という特徴を活した改善方法が
望まれている。However, these methods may not be sufficiently effective in preventing stress corrosion cracking depending on the environment, and there is a need for an improvement method that takes advantage of the high strength of brass as well as its characteristics as a low-cost material with excellent workability. .
本発明はこれに鑑み種々検討の結果、Ｃｕ−Ｚｎ系合金
の優れた加工性と機械的特性を活し、耐応力腐食割れ感
受性を大巾に低減した、耐応力腐食割れ性の優れたＣｕ
−Ｚｎ系合金材料とその製造方法を開発したものである
。In view of this, as a result of various studies, the present invention has developed a Cu-Zn alloy with excellent stress corrosion cracking resistance, which takes advantage of the excellent workability and mechanical properties of the Cu-Zn alloy and significantly reduces stress corrosion cracking susceptibility.
-A Zn-based alloy material and its manufacturing method have been developed.
即ち本発明材料は、Ｃｕ−Ｚｎ系合金からなる芯材の表
面に、芯材よりＣｕ濃度の高い拡散層を形成したことを
特徴とするものである。That is, the material of the present invention is characterized in that a diffusion layer having a higher Cu concentration than the core material is formed on the surface of the core material made of a Cu--Zn alloy.
また本発明製造方法は、Ｃｕ−Ｚｎ系合金を芯材とし、
その表面に芯材よりＣｕ濃度の高いＣｕ又はＣｕ合金を
被覆した後、熱拡散処理を施し、表面に芯材よりＣｕ濃
度の高い拡散層を形成することを特徴とするものである
。Further, the manufacturing method of the present invention uses a Cu-Zn alloy as a core material,
The feature is that the surface is coated with Cu or a Cu alloy having a higher Cu concentration than the core material, and then thermal diffusion treatment is performed to form a diffusion layer on the surface that has a higher Cu concentration than the core material.
本発明は強度と加工性の優れたＣｕ−Ｚｎ系合金、好ま
しくは２０〜３５ｗ（％のＺｎを含有するα黄銅又は丹
銅を芯材とし、その表面に芯材よりＣｕ濃度の高いＣｕ
又はＣｕ合金を被覆した後、熱拡散により表面に芯材よ
りＣｕ濃度の高い拡散層を形成することにより、Ｃｕ−
Ｚｎ系合金の特徴を満し、なおかつＣｕの保護メツキの
みの場合以上に著しく応力腐食割れ感受性を低減したも
のである。熱拡散によるこのような作用の詳細なメカニ
ズムは明らかでないが、表層部が応力腐食割れ感受性の
低い低Ｚｎ濃度合金となると共に、被覆又は後加工によ
る表面欠陥が減少していることが寄与しているものと推
定される。The present invention uses a Cu-Zn alloy with excellent strength and workability, preferably α-brass or red bronze containing 20 to 35% Zn, as a core material, and a Cu-Zn alloy with a higher Cu concentration than the core material on the surface.
Alternatively, after coating a Cu alloy, a diffusion layer with a higher Cu concentration than the core material is formed on the surface by thermal diffusion.
It satisfies the characteristics of Zn-based alloys, and has significantly reduced stress corrosion cracking susceptibility compared to the case of only Cu protective plating. The detailed mechanism of this effect due to thermal diffusion is not clear, but contributing factors include the fact that the surface layer is a low Zn-concentrated alloy with low stress corrosion cracking susceptibility, and that surface defects due to coating or post-processing are reduced. It is estimated that there are.
Ｃｕ−Ｚｎ系合金からなる芯材の表面に被覆するものと
しては、純Ｃｕ又は芯材よりＣｕ濃度の高い銅合金が使
用できる。被覆方法としては湿式メツキ、溶射、蒸着、
クラッド等公知の方法が利用できるが、用途に合せて最
も効率的な方法を用いればよい。被覆層の厚さは５〜２
０μで充分効果が認められ、それ以上厚くしても効果は
飽和し、製造コストが上昇し、工業的には好ましくない
。Pure Cu or a copper alloy having a higher Cu concentration than the core material can be used to coat the surface of the core material made of a Cu--Zn alloy. Coating methods include wet plating, thermal spraying, vapor deposition,
Although known methods such as cladding can be used, it is sufficient to use the most efficient method depending on the purpose. The thickness of the coating layer is 5-2
A sufficient effect is observed with a thickness of 0 μm, and even if the thickness is increased beyond that, the effect will be saturated and the manufacturing cost will increase, which is not desirable from an industrial perspective.
以下本発明を実施例について説明する。The present invention will be described below with reference to Examples.
高周波溶解炉により、Ｃｕ地金を５ｋｇ溶解し、木炭被
覆を施した後、所定のＺｎ量を添加し、第１表に示す組
成のＣｕ−Ｚｎ合金（Ｃｕ −２０〜３５ｗｔ％Ｚｎ）
を鋳造した。この鋳塊に圧延と焼鈍を繰返し施して厚さ
１ｍｍ、巾１００ｍｍの板材とした後、長さ６０ｃａに
切断し、Ａｒ雰囲気中５００℃で１時間焼鈍して軟質材
とした。その後第１図に示すように軟質材としたＣｕ−
Ｚｎ合金板（１）の表面（両面）にＣｕ ｔ２）をメツ
キし、これを加熱拡散処理（３５０〜５５０℃、０．５
〜１０時間）して第２図に示すようにＣｕ−Ｚ ｎ合金
板（１）の表層にＣｕとＺｎの拡散層（３）を形成した
。これについて拡散層における表面のＣｕ濃度とＺｎ濃
度を測定すると共に、応力腐食試験を行なった。その結
果を第１表に示す。After melting 5 kg of Cu metal in a high-frequency melting furnace and coating it with charcoal, a predetermined amount of Zn was added to form a Cu-Zn alloy (Cu -20 to 35 wt% Zn) with the composition shown in Table 1.
was cast. This ingot was repeatedly rolled and annealed to form a plate material with a thickness of 1 mm and a width of 100 mm, which was then cut into a length of 60 ca and annealed at 500° C. for 1 hour in an Ar atmosphere to obtain a soft material. After that, as shown in Fig. 1, Cu-
The surface (both sides) of the Zn alloy plate (1) is plated with Cut2), which is heated and diffused (350-550°C, 0.5
~10 hours) to form a Cu and Zn diffusion layer (3) on the surface layer of the Cu-Zn alloy plate (1) as shown in FIG. Regarding this, the surface Cu concentration and Zn concentration in the diffusion layer were measured, and a stress corrosion test was conducted. The results are shown in Table 1.
腐食割れ試験は、エリクセン試験機により直径６６ｍｍ
φの円板を打抜いた後、高さ３３ｍｍのカップに絞り加
工して残留応力を１８〜２２ｋｇ／ｍ （Ｘ線測定法に
より測定）として行なった。腐食環境は月Ｓ Ｃ８３０
６に準拠し、２ ｖｏ１％のＮＨ３を１０１のデシケー
タ−内に入れてＮＨ３ガスを発生させ、その中に前記カ
ップを入れ、カップに割れが発生するまでの日数を測定
した。Corrosion cracking test was performed using an Erichsen tester with a diameter of 66 mm.
After punching out a disk of φ, it was drawn into a cup having a height of 33 mm, and the residual stress was set to 18 to 22 kg/m (measured by X-ray measurement method). The corrosive environment is Moon SC830
6, 2 vol% NH3 was put into a 101 desiccator to generate NH3 gas, the cup was placed therein, and the number of days until the cup cracked was measured.
尚比較のためＣｕメツキを施さないＣｕＺｎ合金板とＣ
ｕメツキを施した後熱拡散処理を施さないＣｕ−Ｚｎ合
金板について、同様の試験を行ない、その結果を第１表
に併記した。For comparison, CuZn alloy plate without Cu plating and C
Similar tests were conducted on Cu-Zn alloy plates that were U-plated and then not subjected to heat diffusion treatment, and the results are also listed in Table 1.
第１表から明らかなように、本発明材料Ｎα１〜５は応
力腐食割れ感受性が大巾に減少し、耐応力腐食割れ性が
一段と向上することが判る。As is clear from Table 1, it can be seen that the stress corrosion cracking susceptibility of the materials Nα1 to Nα5 of the present invention is greatly reduced, and the stress corrosion cracking resistance is further improved.
これに対し比較材料Ｎα６〜８は従来のＣｕＺｎ合金の
応力腐食割れ感性で、すでに知られている如（、Ｚ ｎ
量の増加と共に応力腐食割れ感受性が高くなっている。On the other hand, the comparative materials Nα6 to 8 are susceptible to stress corrosion cracking of conventional CuZn alloys, as is already known (, Z n
As the amount increases, the stress corrosion cracking susceptibility increases.
また比較材料Ｎα９は従来のＣｕメツキ材料（拡散処理
なし）で比較材料Ｎα７よりはやや応力腐食割れ感受性
が小さくなっているが、不十分であることが判る。Comparative material Nα9 is a conventional Cu-plated material (without diffusion treatment) and has a slightly lower stress corrosion cracking susceptibility than comparative material Nα7, but it is found to be insufficient.
以上本発明材料として軟質材にＣｕメツキを施した後、
熱拡散処理を施した例について説明したが、これに限る
ものではなく、例えば硬質材にＣｕメツキを施し、その
後の焼鈍によって拡散させても同様の効果が得られる。After applying Cu plating to the soft material as the material of the present invention,
Although an example in which thermal diffusion treatment is performed has been described, the present invention is not limited to this. For example, the same effect can be obtained by applying Cu plating to a hard material and then diffusing it by subsequent annealing.
また硬質材を得るためには、拡散処理後、所望の冷間加
工を加えればよい。Further, in order to obtain a hard material, desired cold working may be performed after the diffusion treatment.
このように本発明によれば、Ｃｕ−Ｚｎ系合金の致命的
な欠点である応力腐食割れ感受性を大巾に小さくするこ
とが可能となり、各種の端子、コネクター、配線器具部
品、更には自動車用ラジェータのタンク材やコアプレー
ト祠に使用腰大巾な信頼性を向上することができる等、
工業上顕著な効果を奏するものである。As described above, according to the present invention, it is possible to greatly reduce the stress corrosion cracking susceptibility, which is a fatal drawback of Cu-Zn alloys, and it is possible to significantly reduce the susceptibility to stress corrosion cracking, which is a fatal drawback of Cu-Zn alloys. Can be used for radiator tank materials and core plate shrines to improve reliability, etc.
This has a remarkable industrial effect.
第１図はＣｕ−Ｚｎ合金板のＣｕメツキ状態を示す断面
図、第２図はＣｕメツキ後の熱拡散状態を示す断面図で
ある。
（１）Ｃｕ−Ｚｎ合金板
（２１Ｃｕメツキ層
（３）Ｃｕ＆Ｚｎの拡散層FIG. 1 is a sectional view showing the Cu plating state of a Cu-Zn alloy plate, and FIG. 2 is a sectional view showing the thermal diffusion state after Cu plating. (1) Cu-Zn alloy plate (21Cu plating layer (3) Cu & Zn diffusion layer
Claims (2)
りＣｕ濃度の高い拡散層を形成したことを特徴とする耐
応力腐食割れ性の優れたＣｕ−Ｚｎ系合金材料。(1) A Cu-Zn alloy material with excellent stress corrosion cracking resistance, characterized in that a diffusion layer having a higher Cu concentration than the core material is formed on the surface of a core material made of a Cu-Zn alloy.
りＣｕ濃度の高いＣｕ又はＣｕ合金を被覆した後、熱拡
散処理を施し、表面に芯材よりＣｕ濃度の高い拡散層を
形成することを特徴とする耐応力腐食割れ性の優れたＣ
ｕ−Ｚｎ系合金材料の製造方法。(2) After using a Cu-Zn alloy as a core material and coating its surface with Cu or a Cu alloy that has a higher Cu concentration than the core material, heat diffusion treatment is performed to form a diffusion layer on the surface that has a higher Cu concentration than the core material. C with excellent stress corrosion cracking resistance characterized by the formation of
A method for producing a u-Zn alloy material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27734588A JPH02125830A (en) | 1988-11-04 | 1988-11-04 | Cu-zn series alloy material having excellent stress corrosion cracking resistance and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27734588A JPH02125830A (en) | 1988-11-04 | 1988-11-04 | Cu-zn series alloy material having excellent stress corrosion cracking resistance and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02125830A true JPH02125830A (en) | 1990-05-14 |
Family
ID=17582232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27734588A Pending JPH02125830A (en) | 1988-11-04 | 1988-11-04 | Cu-zn series alloy material having excellent stress corrosion cracking resistance and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02125830A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120297583A1 (en) * | 2009-12-25 | 2012-11-29 | Ykk Corporation | Zipper Component and Slide Zipper, and Method for Producing Zipper Component |
| WO2021025071A1 (en) * | 2019-08-06 | 2021-02-11 | 三菱マテリアル株式会社 | Copper alloy sheet, copper alloy sheet with plating film, and methods for producing these |
-
1988
- 1988-11-04 JP JP27734588A patent/JPH02125830A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120297583A1 (en) * | 2009-12-25 | 2012-11-29 | Ykk Corporation | Zipper Component and Slide Zipper, and Method for Producing Zipper Component |
| WO2021025071A1 (en) * | 2019-08-06 | 2021-02-11 | 三菱マテリアル株式会社 | Copper alloy sheet, copper alloy sheet with plating film, and methods for producing these |
| US11926889B2 (en) | 2019-08-06 | 2024-03-12 | Mitsubishi Materials Corporation | Copper alloy plate, copper alloy plate with plating film, and methods for producing these |
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